PCL

If the titration curve follows the change in concentration for CL, then we calculate pCl as... 

After the equivalence point, pCl and pAg are determined by the concentration of excess Ag+. Using values from Table 9.21, we plot points for 30.0 mb and 40.0 mb of titrant (Figure 9.42d). 

Antimoay peatafluoride is used to saturate double boads ia straight-chain olefias, cycloolefias, aromatic rings (19—21), and ia the fluoriaatioa of halocarboas and CrO CL, MoCL, WCL, PCL, P.O.., SiCL, TiCL, and SiO. ... 

CH2(CF2CH2 2,4, been synthesized by the reaction of PCl and the lithium salt of the respective polyfluoroalkyl alcohols followed by... 

Phosphites. Tertiary phosphites are also commonly used and are particularly effective ia most mixed metal stabilizers at a use level of 0.25—1.0 phr. They can take part ia a number of different reactions duting PVC processing they can react with HCl, displace activated chlorine atoms on the polymer, provide antioxidant functionaHty, and coordinate with the metals to alter the Lewis acidity of the chloride salts. Typical examples of phosphites are triphenyl phosphite [101 -02-0], diphenyl decyl phosphite [3287-06-7], tridecyl phosphite [2929-86-4], and polyphosphites made by reaction of PCl with polyols and capping alcohols. The phosphites are often included in commercial stabilizer packages. 

Various inorganic, organic, and organometaUic compounds are known to cataly2e this polymerization (4,8,9). Among these, BCl is a very effective catalyst, although proprietary catalysts that signiftcandy lower polymerization temperature from the usual, sealed-tube reaction at 250°C are involved in the industrial manufacture of the polymer. A polycondensation process has also been developed for the synthesis of (4) (10—12). This involves elimination of phosphoryl chloride from a monomer prepared from (NH 2 04 and PCl. ... 

The three steps in equation 3 are carried out in one vessel. This affords a wide variety of disilylaminoorganophosphines (8), including those with vinyl substituents (65), in yields of 40—85%. The oxidation of (8) to (9) and the reaction of (9) with alcohol (eq. 4) are carried out in a second reactor to provide the "monomer" phosphoranimines (10) in overall 30—65% yield based on starting PCl or CgH PCl2. The use of in place of Br2 in the conversion of (8) to (9) makes it possible to carry out all the reactions leading to (10) in one vessel, and this has significantly increased yields of the monomer, with overall yields up to 80% (66). 

The remaining 15% of the elemental P is used in P -dependent apphcations which require the element as a direct reactant. The principal products include P2S5, PCl and POCl, 2 5 hypophosphite, with much smaller amounts leading to PH, red P, phosphonates, and various other phosphoms derivatives. Pinal apphcations include flame retardants (qv), lubricant additives, insecticides, herbicides, water treatment, cleaning compounds, plastici2ers, and semiconductors (14). 

The tnhahdes of phosphoms usually are obtained by direct halogenation under controlled conditions, eg, in carbon disulfide solution in the case of the triiodide. Phosphoms trifluoride [7647-19-0] is best made by transhalogenation of PCl using AsF or Cap2. AH of the phosphoms tnhahdes are both Lewis bases and acids. The phosphoms tnhahdes rapidly hydroly2e in water and are volatile. Examination by electron diffraction has confirmed pyramidal stmctures for the gaseous tnhahde molecules (36). Physical properties and heat of formation of some phosphoms hahdes are hsted in Table 7. 

The pentahalides of phosphorus, PX, in the gas phase exhibit varying tendencies to dissociate into trihaUde and halogen. InstabiUty increases with increasing ionic radius of the halogen. The pentafluoride appears to be thermally stable. Dissociation of the pentachloride, a few percent at 100°C and 101.3 kPa (1 atm), is essentially completed at 300°C (36). The pentabromide is partially dissociated in the Hquid state and totally dissociated above ca 35°C (39). Pentaiodide does not exist. The molecules of PF and PCl in the vapor phase are trigonal bipyramids. In the crystalline state, both pentachloride and pentabromide have ionic stmctures, ie, [PClJ IPClg] and [PBr4]" PBrJ , respectively. The PX" 4 cations are tetrahedral and the PX anion is octahedral (36,37). 

Phosphoms haUdes and metals or metal salts form addition complexes. Some typical compounds are PCl iSbCl and PCl iAlCl. The trivalent complexes contain metal—phosphoms bonds. The pentavalent complexes involve rearrangements to produce assembles of tetrahedral PX cations and various anions. 

Phosphoms trichloride, PCl, is a clear, volatile Hquid having a pungent, irritating odor. Principal reactions of PCl, an excellent chlorination reagent for various hydrocarbons, are summarized in Figure 3. 

The reaction of phosphoms trichloride and water is highly exothermic and vigorous. Depending on the mole ratio of H2O/PCl, three different products can result from hydrolysis. If the ratio is greater than 3, phosphonic acid is produced ... 

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